Producing azanthracene derivatives



Patented Oct. 11, 1938 UNITED STATES 2,133,100: V PRODUCING AZANTHRACENEEYDERIVATIVES Karl Koeberle and Ernst Ploetz, Ludwigshafen:

on-the-Rhine, Germanyyassignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware 7 No Drawing. Application July 24, 1934, Serial No. 736,778. In Germany August 5, 1933 6 Claims. (Cl. 260-269) The present invention relates to azanthracene derivatives and a process of producing same.

We have found that azanthracene derivatives are obtained in a simple manner by converting Z-naphthylamines which contain in the l-position a substituent attached to the naphthalene nucleus by means of a CC-linkage such as 1-methyl-, lethyl-, 1-pheny1-, 1-benzyl-, 1-, naphthyl-Z-amino or l-benzoyl-2-amino-naph- 1G thalene into meso substitution products of azanarsenic acid, nitrophenol or picric acid.' I The azanthracene derivatives obtainable in,

good yields and in a state of good purity according to this invention may be substituted according to the usual methods, as for example by treatment with halogen or agents supplying halogen or by treatment with nitrating agents.

The products thus obtainable may be purified by the usual methods, as for example by crystallization, distillation, sublimation or by way of their salts with strong acids. They are valuable intermediate products for the preparation of dyestufis.

The following examples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

Example 1 benzene sulfonic acid sodium salt are boiled.

added until the reaction is slightly acid to congo. The solution filtered from calcium sulfate sludge is rendered alkaline with caustic soda solution. The filtered, washed and dried precipitate yields,

5 by repeated boiling with trichlorbenzene, a good TENT-, F IcE yield of beautifully crystallized 9'-azanthracy1- 9,-azanthrazene which'fdoes not melt at 350 centigrade.

- According to analysis the formula is 'CzeHis-Nz the-percentages being: a

Calculated: 87.61 c;. 4153 7.87 I

Found: 87.85 C; 4.591 12, 77 .86

Example 2;

parts of 2.2'-diamino 1.1-dinaphthyl. are to suspended in a mixture'of 200 parts ofconcen I tratedsulfuric acid with l00parts of water and 37 parts of epichlorhydrinare added while coolr 7 ing. In the course'of two hours a solution of parts of arsenic acid in30 parts of 66 percent heated "to '140"centigra'de. The reaction mixture isheated' at about 140" centigrade for 8-hours.

It is then poured on to ice and worked up inthe manner describedin Example 1. product thus obtained is identical to that obtained according to Example 1. v

Example 3 parts of 1-methyl-2-naphthylamine are heated to 140 centigrade-in a mixture of-fl1500 parts of 64 per cent sulfuric acid and 100 parts -thracene formed isisolated in the manner. de-

scribed in'Example 1. What we claim is: 1

1. A process of producing azanthracene derivatives which comprises heatingj2-naphthylamines' corresponding to the general formula 7 r NH:

sulfuric acid is dropped into the said mixture The reaction- I in which R isa sub stituent of the class consisting ated derivatives in the presence of sulfuric acid and mild oxidizing agents.

2. A process of producing azanthracene derivatives which comprises heating Z-naphthylamines corresponding to the general formula in which-R-is a substituent of the class consisting of alkyl radicals and aryl radicals containing up to two rings attached to the naphthalene nucleus by means of a C--C-linkage with glyc'erine in the presence of sulfuric acid and mild oxidizing agents.

3. A process of producing azanthracene derivatives which comprises heating 2-naphthylamines corresponding to the general formula.

inwhich R. is-a substituent of the class consisting of alkyl radicals and aryl radicals containing up to two rings attached to the naphthalene nucleus by means of a CC-linkage with epichlorhydrin in the presence of sulfuric acid and mild oxidizing agents.

4. A process of producing azanthracene derivatives which comprises heating Z-naphthylamines corresponding to the general formula in which R is a substituent of the-class consisting of alkyl radicals and aryl radicals containing up to two rings attached to the naphthalene nucleus by means of a C-C-linkage with a compound of the group consisting of glycerine and its chlorinated derivatives in the presence of sulfuric acid and a nitro compound of the benzene series.

5. A process of producing azanthracene derivatives which comprises heating 2-naphthylamines corresponding to the general formula in which R'is' a substituent of the class consisting of alkyl radicals andaryl radicals containing up to two rings attached to the naphthalene nucleus by means of-a-C--C-linkage with a compound of thegroup consisting of glycerine and its chlorinated derivatives in the presence of sulfuric acid and meta-nitrobenzene sulfonic acid.

6. A process of producing azanthracene derivatives which comprises heating Z-naphthylamines corresponding to the general formula NHzs 

